Separation of plutonium from uranium



United. States Patent 2,917,382 SEPARATION or ,PLUTONIUM FROM URANIUM Harold M. Feder, Park Forest, and Ralph L. Nuttall, Downers Grove, 111., assignors to the United States of America as represented by the United States Atomic Energy Commission No Drawing. Application August 14, 1957 Serial No. 678,251

8 Claims. (Cl. 7584.1)

This invention deals with a process of separating plutonium from neutron-irradiated uranium.

It has been proposed heretofore to separate plutonium from neutron-irradiated uranium by melting the uranium, mixing the liquid uranium with molten magnesium, and then separating the magnesium which contained the bulk of the plutonium from the liquid uranium. This method, however, showed certain disadvantages The liquid uranium is highly reactive and therefore attacks most of the container materials at the high temperature necessary for maintaining the uranium in the liquid phase. Consequently, the uranium becomes contaminated with the container material. Also, there are only very few materials which are resistant enough to the liquid uranium and thus are suitable for the process. Phase separation was found to be rather diflicult and relatively incomplete, because the interface between the magnesium layer and the radioactive uranium layer had to be determined by remote control.

It is an object of this 'nvention to provide a process uranium in which all of the above-listed disadvantages are overcome. v v Y 1 Itisthus an object of this "invention; to provide a process for the separation of plutonium from neutronirradiated' uranium which can be carried out at a comparatively low temperature so that many materials are available for the equipment in which the process is'to be carried out.

'- It is furthermore an object of this invention to profor the separation of plutonium from neutron-irradiated.

' in situ.

'ture was found tobe sufiicient.

art; filtr..tion with a sintered metallic filter, e.g., of stainless steel, was very satisfactory.

Powdering of the metallic uranium containing the plutonium can be carried out by hydriding as is known to those skilled in the art. Hydriding is best accomplished by heating the uranium in a hydrogen atmosphere at a temperature of about 225 C.; the hydride crumbles off the metallic uranium in the form of a powder as it is formed so that mechanical powdering. is not necessary. The hydride powder may then be decomposed'by heating it in the hydrogen atmosphere at a temperature be tween 350 and 400 C.

Instead of decomposing the uranium and plutonium hydride powder prior to contacting it with the liquid magnesium, the hydride powder can also be introduced as such into the liquid magnesium and decomposed there In fact, this embodiment is preferred, because certain advantages are accomplished thereby. The hydrogen which develops agitates the liquid magnesium so that stirring by mechanical means'becomes unnecessary,

held between 700 and 800 C. This temperature is 7 critical because it is important that theuranium powder does not melt. Contact of the magnesium withthe uranium material for about ten minutes at'this tempera- The magnesium not only extracts the plutonium, but it also removes "a great many rare earth metals, palladium, and other fission products from the uranium.

For recovery of the extracted values from the magnesium, volatilization of the magnesium was found to be the most satisfactory method. This volatilization was preferably carried out under reduced pressure so that alower temperature could be used and attack of the equipment material could be minimized. A temperature of for carrying out the extraction of plutonium and some fission products from the uranium at between 700; and

800 C. Vessels of cast iron, low-carbon steel, and high taken up by the magnesium; and separating the liquid magnesiumfrom the uranium powder.

Leaving the uranium in powder form brings about a more quantitative separation than is obtained from molten uranium, because, in the first place, of course, i

a solid can be removed from a liquid phase more easily than is possible for the separation of two liquid phases, but also, because the solubility of uranium in magnesium and that of magnesium in uranium are relatively low.

It was found that uranium dissolves in magnesium to an amount of between 0.1 and 0.2 percent by weight at a temperature between 1000 and 1 200 C., and that the solubility of magnesium in uranium at about 1150 C. is approximately 0.004 percent by weight. Separation of the magnesium from the uranium powder can be carried out by any means known to those skilled in the chromium steel were found suitable. Chromium-nickelcontaining stainless steel as a rule were found unsuitable, because nickel is soluble in magnesium so'that the steel is attacked during the process; however, stainless 7 steel type No. 347', which is niobium-stabilized steel containing about 18 percent chromium and 8 percent nickel is not-wetted and attacked by magnesium and therefore satisfactory. Other materials applicable are tantalum, titanium, niobium, molybdenum and chromium metals,

and also beryllia, calcium oxide, thoria, urania and zir-' Example I A 36-gram slice of a uranium slug, which contained about 72 ppm. of plutonium, was powdered by hydridlng followed by decomposition of the hydride as set V forth above. The uranium powder was then suspended Paten'ted Dec. 15.,- 1959' in 70 grams of magnesium at.700 C. and maintained therein for three hours. Analyses of the magnesium phase obtained thereby showed that about 80 percent of the plutonium originally present had been extracted um metal containing plutonium with molten magnesium While keeping the uraniumjmetal in solid form whereby the plutonium is taken up by, said magnesiurmand separating the molten magnesium containing said plutonium into the magnesium. The latter alsowas found to confrom the solid uranium metal. tain all of the cerium present. in the uranium. x 2. The process of claim 1 wherein uranium powder E le H is made from uranium metal by heating the metal to xamp 1 about 225 C. in a hydrogen atmosphere and then de- Neutron-irradiated uranium containing fission product composing the hydride thus formed by heating to be elements was converted to a powder by two hydridingtween 350 and 400 C. also in a hydrogen atmosphere. dehydriding cycles. The powder was then suspended 1n 3. The process of claim 1 wherein contacting is carliquid magnesium of 800 C. by mechanical stirring. ried out by dispersing the uranium material powder in The uranium contained 72 ppm. of plutonium. The exthe molten magnesium. traction results are compiled in the table below. 4. The process of claim 1 wherein the molten mag- Run NO.. V 1 2 3 4 Charge: i

- Slug 36.13 g. 25.09 g 22.0 g. 19.11 g. 1 .Mg 70.40 g. 34.20 g 32.26 g. 31.28 g.

Time 3 hrs. 3 hrs. 5% hrs 10min. 2 hrs. min

Per- Mat. Per? Per- Mat. Per- Per- Mat. Per- M t cent BalJ cent cent BaL cent cent BaL cent in Mg. in Mg 111 Mg. in Mg. in Mg. in Mg.

100 0. 07 0. 04. 103 0. 2 0. 4 97 0. 02 9s 90 83 75 93 72 87 91 54 89 93 67 63 97 51 63 90 27 10s 85 12 11 9s 10 13 91 0.2 89 '134 95 105 88 50 91 85 97 10s as 29 100 9 23 102 0. 9 99 1 116 0. 0. 3 120 0. 7 1. 1 97 1. 3 s1 89 0.08 0. 06 104 0 1 0.4 92 0.2 83

1 Mat. Bal.=Material Balance=1001u activity in filtration rcsidue+activity in filtrate It is obvious from the above data that the extraction of a large fraction of the plutonium and rare earth activities proceeds very rapidly with the exception of that of strontium and cesium. It is possible that the readily extractable elements hat/emigrated to grain boundaries as'a re'sult of low-temperature hydriding-dehydriding cycles and so are more easily available to the magnesium solvent. More than one-half of the plutonium was found to be extracted in ten minutes, a longer contact then increasing the plutonium extraction to approximately 90 percent.

The next example illustrates the uranium recovery from an alloy containing plutonium in macro-amounts.

' Example 111 A piece of a uranium-base alloy weighing 51.102

grams, one percent by weight of which was plutonium, was hydrided, and the powder was then heated While in contact with 10.470 grams of magnesium at 800 C. for one hour. The amount of plutonium extracted into the magnesium was found to be 48 percent in regard to the pressure for volatilization of the magnesium. and puriquantity originally present, while only 0.001 percent of I the uranium was extracted. 7

It will be understood that this invention is not to be limited to the details given herein but that it may be modified within the scope of the appended claims.

What is claimed is:

1. A process of extracting plutonium values from a uranium metal comprising contacting powdered uranification'of the plutonium. 1 1 y p y 7. The process of claim 6 wherein thevolatilization temperature is about 725 C. s. 1 1

1 .8. A process of removingplutonium from neutronirradiated uranium metal comprising heating said .uranie um metal at about 225 C. in a hydrogen atmosphere whereby powdered uranium hydride is formed,incorp0- rating said uranium hydride into molten magnesium having a temperature of between 700and 800 C. Whereby the hydride is decomposed to metallic powdered uranium and the plutonium contained in said uranium is takenup by said magnesium; and separating said plutonium-contaming magnesium from the uranium powder. by filtratlon. 1

International Conf. on Peaceful Uses of Atomic En ergy, 1955, vol. 9, page 581. 

1. A PROCESS OF EXTRACTING PLUTONIUM VALUES FROM A URANIUM METAL COMPRISING CONTACTING POWDERED URANIUM METAL CONTAINING PLUTONIUM WITH MOLTEN MAGNESIUM WHILE KEEPING THE URANIUM METAL IN SOLID FORM WHEREBY THE PLUTONIUM IS TAKEN UP BY SAID MGNESIUM; AN SEPARATING THE MOLTEN MAGNESIUM CONTAINING SAID PLUTONIUM FROM THE SOLID URANIUM METAL. 